WO2023095613A1 - イミド結合及び重合性不飽和結合含有環状オルガノシロキサン、及びそれを含む硬化性樹脂組成物 - Google Patents

イミド結合及び重合性不飽和結合含有環状オルガノシロキサン、及びそれを含む硬化性樹脂組成物 Download PDF

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WO2023095613A1
WO2023095613A1 PCT/JP2022/041669 JP2022041669W WO2023095613A1 WO 2023095613 A1 WO2023095613 A1 WO 2023095613A1 JP 2022041669 W JP2022041669 W JP 2022041669W WO 2023095613 A1 WO2023095613 A1 WO 2023095613A1
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bond
polymerizable unsaturated
cyclic organosiloxane
resin composition
bis
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PCT/JP2022/041669
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English (en)
French (fr)
Japanese (ja)
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和弘 土田
将史 藤田
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信越化学工業株式会社
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Priority to CN202280075953.7A priority Critical patent/CN118251445A/zh
Priority to KR1020247020545A priority patent/KR20240114749A/ko
Publication of WO2023095613A1 publication Critical patent/WO2023095613A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors

Definitions

  • the present invention relates to an imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane, and a curable resin composition containing the same.
  • Excellent mechanical properties are required for materials used in sealing materials for electronic parts, prepregs, metal foil-clad laminates, printed wiring boards, and semiconductor packages. .
  • Patent Documents 1 and 2 below report a curable resin composition containing a linear dimethylpolysiloxane having maleimide bonds at both ends and a cyanate ester compound. By introducing a dimethylpolysiloxane structure into the material, these are aimed at obtaining a cured product that has both a coefficient of thermal expansion, hardness and bending strength, but there is room for improvement in terms of performance. was what remained.
  • the present invention has been made in view of the above circumstances, and provides a cyclic organosiloxane containing an imide bond and a polymerizable unsaturated bond, which gives a cured product having excellent hardness and bending resistance, and a curable resin composition containing the same.
  • the purpose is to
  • a curable resin composition containing an imide bond and a polymerizable unsaturated bond-containing cyclic organosiloxane has both hardness, crack resistance and bending resistance. We have found that it is possible, and have completed the present invention.
  • the present invention provides the following imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane, and a curable resin composition containing the same.
  • An imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane represented by the following general formula (1).
  • each R 1 independently represents a monovalent hydrocarbon group or hydrogen atom which may be interposed by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms, and Z is each independently Then, at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms may intervene, a monovalent organic group having an imide bond and a polymerizable unsaturated bond, n is an integer of 2 to 6 , m is an integer from 0 to 4, and the sum of n+m is from 4 to 6.
  • the arrangement of the siloxane units in parentheses may be arbitrary.
  • a curable resin composition comprising (A) the imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane according to any one of 1 to 4 above, and (B) a cyanate ester compound. 6. 6. The curable resin composition as described in 5 above, which further contains a maleimide compound other than the component (A) as the component (C). 7. 7. The curable resin composition according to 5 or 6 above, which further contains (D) a curing catalyst.
  • the imide bond-containing cyclic organosiloxane according to the present invention is represented by the following formula (1).
  • each R 1 independently represents a monovalent hydrocarbon group or hydrogen atom which may be interposed by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms, and Z is each independently Then, at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms may intervene, a monovalent organic group having an imide bond and a polymerizable unsaturated bond, n is an integer of 2 to 6 , m is an integer from 0 to 4, and the sum of n+m is from 4 to 6.
  • the arrangement of the siloxane units in parentheses may be arbitrary.
  • the monovalent hydrocarbon group for R 1 may be linear, branched, or cyclic, preferably having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and cyclohexyl. , heptyl, octyl and decyl groups; alkenyl groups such as vinyl, allyl and butenyl groups; aryl groups such as phenyl, tolyl, xylyl and naphthyl groups; aralkyl groups such as benzyl, phenylethyl and phenylpropyl groups. mentioned. Among these, a methyl group, an ethyl group, and a propyl group are preferable from the viewpoint of the market availability of raw materials to be used.
  • Preferred specific examples of the monovalent organic group having an imide bond and a polymerizable unsaturated bond for Z include groups represented by the following formula (2).
  • R 2 and R 3 are each independently monovalent, which may be interposed by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms. or a hydrogen atom, and R 2 and R 3 may be linked to form a ring structure, a is an integer of 3 to 8, and b is an integer of 0 to 2.
  • More specific structures of such a monovalent organic group having an imide bond and a polymerizable unsaturated bond include, but are not limited to, groups represented by the following formulas (3) and (4). not something.
  • n is preferably 2 to 4, more preferably 2.
  • m is preferably 0 to 2, more preferably 2.
  • the imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane of the present invention includes, for example, a primary amino group-containing cyclic organosiloxane represented by the following formula (5), a cyclic carboxylic acid anhydride group, and a polymerizable carbon-carbon di It can be obtained by imidation reaction with a compound having a heavy bond in the same molecule.
  • R 1 , n, and m have the same meanings as above, and the arrangement of the siloxane units in parentheses may be arbitrary.
  • A is a monovalent organic group having a primary amino group which may be interposed by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms; specific examples of A are 3-aminopropyl group, 6 -aminohexyl group, 8-aminooctyl group and the like.
  • the above primary amino group-containing cyclic organosiloxane can be obtained, for example, by hydrosilylation by reacting the Si—H group of the cyclic organohydrogensiloxane with an amine having a polymerizable carbon-carbon double bond.
  • cyclic organohydrogensiloxane examples include those represented by the following formula (5').
  • R 1 , n, and m have the same meanings as above, and the arrangement of the siloxane units in parentheses may be arbitrary.
  • cyclic organohydrogensiloxanes include 1,3,5,7-tetramethyl-1,3-dipropylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,5- dipropylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and the like.
  • amine having a polymerizable carbon-carbon double bond examples include allylamine, 5-hexenylamine, 7-octenylamine, etc., and the hydrocarbon moiety thereof is selected from oxygen, nitrogen, sulfur and phosphorus atoms. At least one may intervene.
  • the above hydrosilylation is usually carried out in the presence of a catalyst.
  • the catalyst includes known platinum group metal catalysts such as platinum, palladium and rhodium catalysts, with platinum catalysts being preferred.
  • platinum-based metal catalysts include platinum black; solid platinum supported on carriers such as alumina and silica; chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and olefins; complexes and the like.
  • the temperature of the above hydrosilylation reaction may generally be from room temperature to 200°C, preferably from 30 to 120°C.
  • the reaction time can be appropriately determined according to the production scale and reaction temperature.
  • a solvent may not be used, or if necessary, a solvent may be used as long as it does not adversely affect the reaction.
  • the compound having a cyclic carboxylic anhydride group and a polymerizable carbon-carbon double bond in the same molecule is not particularly limited, but from the viewpoint of market availability, maleic anhydride, 1,2,3 ,6-tetrahydrophthalic anhydride and 5-norbornene-2,3-dicarboxylic anhydride.
  • the acid in the compound having a cyclic carboxylic anhydride group and a polymerizable carbon-carbon double bond in the same molecule per 1 mol of the primary amino group in the primary amino group-containing cyclic organosiloxane is preferably 0.8 to 1.5 mol.
  • the reaction time of the above imidization reaction may be any time as long as the raw materials are sufficiently consumed as the reaction progresses, and from the viewpoint of production efficiency, it is preferably 10 minutes to 24 hours, more preferably 1 to 10 hours. More preferably, it is 2 to 7 hours. Further, the reaction temperature is preferably low as long as the desired reaction proceeds and productivity is not impaired.
  • an organic solvent, catalyst, or dehydrating agent may be used as necessary.
  • the organic solvent is not particularly limited as long as it can sufficiently dissolve the raw material without reacting with the raw material.
  • 3-dimethyl 2-imidazolidinone aprotic polar solvents such as N-methylpyrrolidone; sulfones such as tetramethylene sulfone; tetrahydrofuran, 4-methyltetrahydropyran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether mono ether solvents such as acetate and cyclopentyl methyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; and aromatic solvents such as toluene and xylene.
  • ether solvents and aprotic polar solvents are preferred from the viewpoint of reactivity and solubility.
  • An organic solvent can be used individually by 1 type or in mixture of 2
  • the catalyst is not particularly limited, but may be organometallic salts such as tin octylate, zinc octylate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, and tin oleate; metals such as zinc chloride, aluminum chloride, and tin chloride.
  • organometallic salts such as tin octylate, zinc octylate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, and tin oleate
  • metals such as zinc chloride, aluminum chloride, and tin chloride.
  • Examples include chlorides and tertiary amine compounds.
  • cobalt naphthenate is preferred in thermal imidization without using a dehydrating agent from the viewpoint of reactivity, and tertiary amine is preferred in combination with a dehydrating agent to be described later for chemical imidization.
  • dehydrating agent Compared to thermal imidization, chemical imidization using a dehydrating agent has the advantage of being able to lower the reaction temperature of the imidization reaction.
  • dehydrating agents include carboxylic anhydrides, and specific examples include acetic anhydride, propionic anhydride, and succinic anhydride, but are not limited to these.
  • carboxylic anhydride it is preferable to use the carboxylic anhydride and an equimolar amount of a tertiary amine together.
  • the tertiary amine is not particularly limited, triethylamine is preferred from the viewpoint of market availability and ease of removal in the post-process.
  • the amount of the dehydrating agent to be used in chemical imidization from the viewpoint of productivity, it is preferable to use 1 to 2 mol, more preferably 1. to 1 mol of the primary amino group in the primary amino group-containing cyclic organosiloxane. It ranges from 2 to 1.6 mol.
  • the weight average molecular weight of the imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane of the present invention is not particularly limited, but the cured product obtained by curing the curable resin composition containing the compound is sufficiently In consideration of imparting sufficient hardness and flex resistance, the weight average molecular weight is preferably 500 to 5,000, more preferably 600 to 3,000.
  • the weight-average molecular weight in the present invention is a standard polystyrene conversion value determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a developing solvent.
  • the functional group equivalent of the polymerizable unsaturated bond-containing group of the imide bond and polymerizable unsaturated bond-containing cyclic organosiloxane of the present invention is not particularly limited, but the curable resin composition containing the compound is cured. 200 to 500 g/mol is preferable in consideration of imparting sufficient hardness and bending resistance to the cured product obtained by the above.
  • the curable resin composition of the present invention comprises the following components (A) and (B), It contains (A) an imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane, and (B) a cyanate ester compound.
  • the (A) cyclic organosiloxane containing imide bonds and polymerizable unsaturated bonds contained in the curable resin composition of the present invention is the same as the cyclic organosiloxane containing imide bonds and polymerizable unsaturated bonds described above.
  • the content of the cyclic organosiloxane containing an imide bond and a polymerizable unsaturated bond in component (A) can be appropriately set according to the desired properties, and is not particularly limited. From the viewpoint of further improving the physical property balance of 100 parts by mass of the resin solid content in the resin composition, it is preferably 1 to 25 parts by mass, more preferably 2 to 20 parts by mass, and still more preferably 5 to 15 parts by mass. Department.
  • the (B) cyanate ester compound contained in the curable resin composition of the present invention is not particularly limited as long as it is a compound having at least one cyanato group (cyanate ester group), but an aromatic cyanate ester compound is preferred.
  • a curable resin composition using a cyanate ester compound has excellent properties such as heat resistance and low thermal expansion when cured.
  • aromatic cyanate compounds include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1-cyanato-2-, 1-cyanato -3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1-cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2-(4-cyanaphenyl)-2- Phenylpropane (cyanate of 4- ⁇ -cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-2- or 1-cyanato-3-chloro
  • the content of the cyanate ester compound of component (B) can be appropriately set according to the desired properties, and is not particularly limited, but bending strength, dielectric properties, heat resistance, coefficient of thermal expansion, and thermal conductivity. From the viewpoint of further improving the physical property balance of the resin composition, it is preferably 1 to 99 parts by mass, more preferably 10 to 80 parts by mass, and still more preferably 25 to 70 parts by mass, relative to 100 parts by mass of the solid content in the resin composition. is.
  • the curable resin composition of the present invention may further contain a maleimide compound other than component (A) as component (C) and a curing catalyst as component (D), if necessary.
  • maleimide compound of component (C) examples include compounds having two or more maleimide bonds in the molecule, which are generally distributed as bismaleimide resins.
  • a cocondensation product of bismaleimide and an aldehyde compound can be mentioned, and one or more of these can be used.
  • the bismaleimide examples include 4,4'-diphenylmethanebismaleimide, N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-m-phenylenebismaleimide, N,N'.
  • curing catalysts for component (D) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, and the like.
  • Imidazole compounds triethylamine, benzyldimethylamine, ⁇ -methylbenzyldimethylamine, tertiary amine compounds such as 1,8-diazabicyclo[5.4.0]undecene-7; triphenylphosphine, tributylphosphine, tri(p- organic phosphorus compounds such as methylphenyl)phosphine, tri(nonylphenyl)phosphine, triphenylphosphine/triphenylborate, tetraphenylphosphine/tetraphenylborate, tributylhexadecylphosphonium bromide, and tris(dimethoxyphenyl)phosphine; triphenylphosphine, Phosphonium salts obtained by reacting organic phosphorus compounds such as tributylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phos
  • the content of the curing catalyst of component (D) is not limited as long as it satisfies the desired curing speed, cured physical properties, and appropriate pot life of the composition. It is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin solid content.
  • the curable resin composition of the present invention can contain an organic solvent as necessary.
  • an organic solvent can be used individually by 1 type or in mixture of 2 or more types as appropriate.
  • organic solvent any known organic solvent can be appropriately used as long as it is capable of dissolving or compatible with at least part, preferably all, of the various resin components described above, and the type thereof is not particularly limited.
  • organic solvents include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; methyl lactate, methyl acetate, ethyl acetate, butyl acetate and isoamyl acetate.
  • Ester solvents such as ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; polar solvents such as amides such as N-methylpyrrolidinone, dimethylacetamide, and dimethylformamide; aromatic hydrocarbons such as toluene and xylene.
  • Non-polar solvents are mentioned.
  • N-methylpyrrolidinone is preferable from the viewpoint of dissolving power
  • methyl ethyl ketone and the like are preferable from the viewpoint of drying property.
  • the curable resin composition of the present invention can be appropriately prepared according to a conventional method, and the above (A) imide bond and polymerizable unsaturated bond-containing cyclic organosiloxane, (B) a cyanate ester compound, and the above other
  • the preparation method is not particularly limited as long as it is a method for obtaining a curable resin composition uniformly containing the components.
  • the curable resin composition of the present embodiment can be easily prepared by sequentially blending the components (A), (B) and other components in an organic solvent and sufficiently stirring the mixture.
  • the set temperature for heat-curing the curable resin composition of the present invention is not particularly limited as long as the physical properties of the desired cured product can be expressed. to 250°C, more preferably 150 to 200°C.
  • the curing time can be appropriately set.
  • the method for producing the cured product of the curable resin composition of the present invention is not particularly limited, and known production methods can be employed. Examples thereof include a method using a mold and a film forming method by a casting method in which a film provided with a release layer in advance is coated and cured to form a film, but the method is not limited to these.
  • the material of the mold is not particularly limited as long as it can be separated from the cured product obtained after curing.
  • it may be made of metal, glass, plastic, silicone, etc., but it is preferable to use a mold treated with Teflon (registered trademark).
  • Teflon registered trademark
  • Such a mold treated with Teflon (registered trademark) has excellent releasability. Its occurrence can be suppressed.
  • the cured product of the curable resin composition of the present invention is particularly suitable for use as a sealing material for electronic parts, a prepreg, a metal foil-clad laminate, a printed wiring board, and a constituent material for a semiconductor package.
  • a prepreg can be obtained by impregnating or applying the curable resin composition of the present invention to a substrate and drying the substrate.
  • the drying conditions can be, for example, a temperature of 20 to 150 for 1 to 90 minutes.
  • a build-up film or dry film solder resist can be obtained by using a peelable plastic film as a substrate, applying the curable resin composition of the present invention to the plastic film, and drying it.
  • the curable resin composition of the present invention can be used in an uncured state by simply drying the organic solvent, or can be used in a semi-cured (B-staged) state as necessary. can also
  • the temperature of the reaction solution was increased by the dropping reaction, and the temperature was controlled by cooling with air or water so that the reaction progressed within the range of 80 to 90°C. After completion of the dropwise addition, the mixture was heated and stirred at 80° C.
  • A1 had a kinematic viscosity of 33 mm 2 /s at 25° C. and a functional group content of primary amino groups of 253 g/mol. 1 H-NMR and GPC analysis confirmed that A1 was a mixture of a compound represented by the following formula (6) and a compound represented by the following formula (7).
  • the dropping reaction generated heat, and the temperature of the reaction solution was controlled using a water bath so that the temperature did not exceed 50°C. After the dropwise addition was completed, stirring was continued for 1 hour at room temperature, and disappearance of the reaction raw material was confirmed by GPC. Subsequently, 150 parts by mass (1.5 mol) of acetic anhydride was put into the mixture and stirred, and then 150 parts by mass (1.5 mol) of triethylamine was added dropwise. With the dropwise addition, slight heat was generated and the appearance changed from orange to deep red.
  • Example 2 A black oily compound (M2) was obtained in the same manner as in Example 1 except that A1 was changed to A2 (1 mol as an amino group). The viscosity of this compound at 25° C. was 105,000 mPa ⁇ s. 1 H-NMR and GPC analysis confirmed that M2 was a compound represented by the following formula (11).
  • Example 3 A black oily compound (M3) was obtained in the same manner as in Example 1 except that maleic anhydride was changed to 5-norbornene-2,3-dicarboxylic anhydride (1 mol). The viscosity of this compound at 25° C. was 52,000 mPa ⁇ s. 1 H-NMR and GPC analysis confirmed that M3 was a mixture of a compound represented by the following formula (12) and a compound represented by the following formula (13).
  • MR-0 A disiloxane having two maleimide bonds represented by the following formula, synthesized according to "Synthesis Example 2" described in WO 2019/39135.
  • BMI-70 an aromatic compound having two maleimide bonds represented by the following formula (manufactured by K.I Kasei Co., Ltd., trade name “BMI-70”)
  • BMI-70 aromatic compound having two maleimide bonds represented by the following formula (manufactured by K.I Kasei Co., Ltd., trade name “BMI-70”)
  • LECY 2,2-bis(4-cyanatophenyl)ethane represented by the following formula (manufactured by Lonza Japan, trade name “Primaset (registered trademark) LECy”)
  • Curing catalyst tetraphenylphosphonium tetraphenylborate (manufactured by Hokko Chemical Industry Co., Ltd., "TPP-K)
  • thermosetting resin composition in Table 1 After pouring the thermosetting resin composition in Table 1 into a Teflon (registered trademark) mold (depth 0.3 mm ⁇ length 15 cm ⁇ width 10 cm), the mold was placed on a hot plate heated to 200 ° C. was allowed to stand, and the organic solvent N-methylpyrrolidinone (NMP) was volatilized over 90 minutes at 200°C. Thereafter, the mold was heated in a dryer at 150° C. for 60 minutes, and further heated in a dryer at 200° C. for 60 minutes to complete curing, thereby obtaining a sheet molding.
  • NMP organic solvent N-methylpyrrolidinone
  • the sheet moldings obtained in Examples 4 to 8 and Comparative Examples 1 to 7 were evaluated as follows. Table 2 shows the results. (1) Appearance The sheet molding (test piece) obtained above was visually observed to determine the presence or absence of abnormality. ⁇ : No abnormality ⁇ : Abnormality such as tack, spots, cracks, etc. (2) Formability Observation was made to see if the sheet would stand on its own when removed from the mold, and the following judgments were made. O: It is possible to take out as a sheet without any abnormality. x: Brittle or soft, impossible to take out as a sheet.
  • the sheets obtained in Examples 4 to 8 were excellent in moldability, bending resistance, storage elastic modulus and durometer hardness.
  • the resin composition of Comparative Example 1 did not contain a siloxane-based maleimide and had a high cross-linking density of the sheet, so that the resulting test piece lacked bending resistance.
  • the resin composition of Comparative Example 3 exhibited bending resistance derived from the straight-chain dimethylpolysiloxane structure, the hardness was lowered.
  • the resin composition of Comparative Example 7 uses an aromatic maleimide in combination.
  • the cured product using the imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane of the present invention achieves both desired hardness and excellent bending resistance, and can be used for sealing electronic parts. It can be suitably used for sealing materials, prepregs, metal foil-clad laminates, printed wiring boards, semiconductor package constituent materials, and the like.
  • the present invention is not limited to the above embodiments.
  • the above embodiment is merely an example, and any device that has substantially the same configuration as the technical idea described in the claims of the present invention and produces the same effect is the present invention. It is included in the technical scope of the invention.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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PCT/JP2022/041669 2021-11-25 2022-11-09 イミド結合及び重合性不飽和結合含有環状オルガノシロキサン、及びそれを含む硬化性樹脂組成物 WO2023095613A1 (ja)

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CN202280075953.7A CN118251445A (zh) 2021-11-25 2022-11-09 含有酰亚胺键和聚合性不饱和键的环状有机硅氧烷和包含其的固化性树脂组合物
KR1020247020545A KR20240114749A (ko) 2021-11-25 2022-11-09 이미드 결합 및 중합성 불포화 결합 함유 환상 오르가노실록산, 및 그것을 포함하는 경화성 수지 조성물

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JP2012149196A (ja) * 2011-01-21 2012-08-09 Jnc Corp 熱硬化性組成物、硬化膜、及び表示素子
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